JPS6191267A - Production and use of pigment mixture based on perylene tetracarboxylic diimide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to perylenetetracarboxylic acid-bis3/, S
/-Process for preparing a mixed crystal preparation based on perylenetetracarboxylic acid diimide in the α-modified crystal lattice of dimethylphenylimide, and use of the mixed crystal preparation thus obtained for coloring organic polymers Regarding the method.

For use in highly melting synthetic resins, pigments must not only have high sunlight fastness and weather resistance, but also color printing F) (
It should have sufficient thermal stability to withstand the processing temperatures of the Farbeindruck.

The range of available organic pigments for highly melting synthetic polymers, in particular polyolefins, is of great interest for this field of use in terms of organic colorants as an alternative to the cadmium-pigments traditionally mainly used. It is incomplete due to the demand.

In order to obtain clear red tones, perylene pigments of the formula (1) have long been found to be suitable for this field of use. These compounds obtained according to German Pat.
No. 2 and EP 23191 No. 8 (U.S. Pat. No. 4,404,385), the -12 obtained in the crystalline phase, referred to as α-modification, transitions to a fine pigment form (e.g. perturbed ball milling or #i After conventional grinding in a roll mill) it gives a clear, tight red dyeing with high tinting strength and good thermal stability (8:1).

The increasing use of high melting polymers such as polypropylene and the trend towards higher production rates in the case of synthetic resin articles
In recent years, the intensification of heat loads has led to the demand for further increasing the heat resistance of this material.

Additionally, there has long been a demand from many plastics processors for distinct yellow colors and strong red colors with excellent fastness levels.

Perile/tetracarboxylic acid bis-4'-nitoxyphenylimide represented by formula (3), which has been known for a long time, can be used in such a bright yellowish red color. However, the undesirable thermal stability of this pigment precludes its use in highly melting polymers, which undergo a color change to blue-red at high processing temperatures.

The present inventor mainly obtained symmetric perylenetetracarboxylic acid-bis-3', dimethyl, represented by the following formula (1) (in the formula, R1-j represents a methyl or ethyl group) by the following method. Phenylimide and at least one of the above formula (2)
perylenetetracarboxylic acid diimide-mixed crystal pigment in the α-modified crystal lattice of perylenetetracarboxylic acid-bis-3',5'-dimethylphenylimide of formula (1) consisting of an asymmetrically disposed diimide of It was discovered that it is possible to produce That is, 1 mole of perylenetetracarboxylic dianhydride is combined with an excess of 3,5-dimethylaniline up to 3 mol/L/- which amounts to a total of 0.5-6% by weight of 4-
It is condensed with ethoxyaniline and/or Fi4-containing methoxyaniline.

Perylenetetracarboxylic acid diimide obtained in this way~
Mixed-crystal pigments show a marked improvement in high-melting polymers, especially polyethylene and polypropylene, after conversion to a fine-grained form by conventional finishing methods, e.g. milling, compared to the pure pigments of the formula (1) described. It also provides excellent thermal stability and, especially when the mixed crystal component of formula (2) contains ethoxy groups, a coloration with the desired yellowish hue. The intensity of yellow flame can be controlled by changing the number of 4-ethoxyaniline in 3,5-dimethylaniline. RR can also be achieved with a slightly more pronounced color shift to yellowish red with dd-methoxyaniline.

Perylenetetracarboxylic acid-pis-5' of formula (1).

The crystalline modification (“α-modification”) of 5′-dimethylphenylimide has the X-ray diffraction pattern shown in FIG.
The figure shows the Xi diffraction pattern of a typical mixed crystal obtained by the present invention. As can be seen, the X-ray diffraction patterns are identical and therefore the crystal lattices are identical.
Add at least 2 moles of 3,5-dimethylaniline to the molar solution. 3,5-dimethylaniline 4-1 for my sister
6 moles of excess] force 2 is used. It is true that a large excess of 3,5-dimethylaniline is possible, but it is of little use for economic reasons.

The preferred content of 3,5-dimethylaniline in 4-ethoxy-aniline and/or 4-methoxyaniline is about 1
The amount ranges from about 3i￥r to about 3i￥r. In particular, 4-ethoxyaniline can be used.

The cocondensation reaction can be carried out by known methods, for example as described in German Patent No. 11 050.
85 (UK Patent No. 897,707), German Patent Application No. 1094897 or German Patent Application No. in the presence of condensation accelerators such as zinc chloride, zinc carboxylates or mineral acids in high-boiling solvents such as di-trichlorobenzene, nitrobenzene, N-methylpyrrolidone, quinoline, phenol or in excess of 3,5-dimethylaniline. Among these, it can be carried out by reacting.

The reaction product can be separated in the customary manner by filtration, optionally after predilution with a low-boiling alcohol, such as methanol. The composition of the mixed crystal reaction product obtained is 3,5-
It depends on the content of 4-alkoxyaniline in dimethylaniline and the excess of 5,5-dimethylaniline used.

It consists primarily of about 99-70 mole percent of the symmetric diimide of formula (1) and about 1-30 mole of the asymmetric diimide of formula (2).

It is mainly composed of about 99-85 mol% of the symmetric diimide of formula (1) and about 1-15 mol% of the asymmetric diimide of formula (2), and a mixture in which the substituent R in formula (2) is an ethyl group. The resulting dry crude pigment, which is preferably a crystalline compound, is converted into a finely divided transparent colored pigment form by grinding by conventional grinding methods, for example in a moving ball mill or roll mill, in the presence of grinding aids. can. In this case, steel balls or corundum balls are generally used as the crushed bodies. The grinding aid can be a water-soluble salt, such as sodium sulfate, aluminum sulfate or l'i sodium chloride, which can be separated from the pigment by aqueous salt extraction in known manner after the grinding has ended.

Perylenetetracarboxylic acid diimide-based mixed crystal pigments are already known. US Pat. No. 3,554,776 discloses a pigment comprising a solid solution of at least two perylenetetracarboxylic acid diimides.

The compound on which this pigment is based has N symmetry.

N'-substituted perylenetetracarboxylic acid diimide. In contrast, the mixed crystals according to the invention, in which the component of formula (2) is an asymmetrically substituted diimide, differ in their different chemical composition. This is published in German Patent Application No. 2009073 (Canadian Patent No. 912,7
This also applies to the perylenetetracarboxylic acid diimide-pigment solution, which is known from Patent No. 57). This pigment is also a mixture consisting of symmetric lJ, IJ'-image berylenetetracarboxylic acid diimide.

It can be expected that in addition to the symmetrically substituted perylimide of formula (1), only the asymmetrically substituted perylimide of formula (2) will be produced in the cocondensation reaction according to the present invention. There wasn't.

The novel mixed crystal pigments obtainable according to the invention are useful for pigmenting paints, synthetic resins such as polyvinyl chloride, polystyrene, polyamides, and particularly preferably for pigmenting high-melting polymers such as polyethylene and polypropylene and polypropylene. Suitable for spinning and dyeing. The present pigments are described, for example, in German Patent No. 1,067,157 (US Pat. No. 2,905,685).
It has the same crystal modification compared to the perylene pigment of the formula (1) described in the paper No. MJ) 2, and after a corresponding transition to a fine and transparent pigment form, it has a rich melting point of organic heavy The combination has at least the same tinting strength and remarkable back-in heat resistance in more yellow tones, especially in polyolefins.

German Patent Application Publication No. 2832761 (U.S. Patent No. 4262851) and European Patent No. 42819
The present pigment has a significantly yellower, clearer tone than the opaquely pigmented, bisoxy, rigid pigment form of formula (1) described, known from U.S. Pat. No. 4,404,386. In the legal examples, unless otherwise specified, the X-ray diffraction pattern (expressed as a percentage) refers to the amount of V. 2
-Write with a line.

Is the mass spectrum recorded by KRATO8's double companion material?
- Performed using a spectrometer h (s5o (electron impact ionization 70θV, 380°C), Example 1 Perylenetetracarboxylic dianhydride 62.0.!9 (0
, 158 mol) and 200 g of 5,5-dimethylaniline (
1.55 mol), 4-ethoxyaniline 2.1.9 (o
, o15 mol) and 466 g of quinoline with stirring for 7 hours after addition of 4.39 g of red water zinc chloride.
Keep at ℃. The precipitated reaction product is filtered off with suction at 100° C. and subsequently washed first with methanol, then twice with hydrochloric acid and finally with water until neutral. Then filter cake 2
Wash with caustic potash solution until the effluent filtrate is colorless and with water until neutral and dry. Pure yellowish-red, uniformly crystalline cocondensation product of α-modification (Fig. 2 span)
93.3.9 is obtained.

In addition to the main mass peak M+598 (component of formula (1)), the mass spectrum has a mass peak of an asymmetric component (formula 2)! ”6
The molecular mass of the symmetrical compound (formula 3), clearly showing +4, is 63
o cannot be observed.

To convert the cocondensation product into fine pigmented form, 3ag of the co-condensation product was mixed with 150.9ml of anhydrous sodium sulfate on a vibrating test stand with 140g of corundum balls (diameter 12n).
The ground material was ground for 6 hours in a synthetic resin grinding container, and the ground product was extracted with aqueous salt, dried, and then processed into an IK-cross hammer mill (JA
(of NKK and KUNKFiL) (the products obtained according to the following examples are likewise ground).

Example 2 Perylenetetracarboxylic dianhydride 39.2g (0,1
mol), anhydrous zinc chloride 2.0 g, 3,5-dimethylaniline 121. ji+(1,0-1 nyl), quinoline 20
02 and 4-ethoxyaniline 2.75.9 (0,02
mol) is stirred for 8 hours at 180-185°C. The resulting homogeneously crystalline reaction product is isolated as described in Example 1. α-modified red mixed crystals s s, s g are obtained, the mass spectrum clearly shows mass peak M”598 (component of formula (1)) and mass peak M+614 (component of formula (2)), formula Molecular quality of compound (3) fk6
501-i Not observed.

Example 3 2.71% 4-ethoxyaniline and 96% phenol
．． 3,5-dimethoxyaniline containing 8999.5
9 @ suspension of perylenetetracarboxylic dianhydride 39.29 (0.1 mol) in (0.8 mol) t″ 8 hours 17
The reaction is carried out at 5-180°C. After conventional isolation, 59.1 g of a yellowish-red cocondensation product of the α-crystalline modification are obtained. The mass spectrum shows mass peak M+598 (component of formula (1)) and mass peak M+614 (component of formula (2)). It can be observed only in the molecular mass range of 630 ij of the compound of formula (3).

Example 4 Perylenetetracarboxylic dianhydride 39.2.9 3,
5-dimethylaniline 4B, 49% 4-methoxyaniline 3.1g, quinoli 7200g and anhydrous zinc chloride4.
1.9 of the α-crystal modification after the usual work-up reaction at 180-190° C. for 10 hours in a mixture consisting of 59.
Get rid of 39.

Example 5 Berylenetetracarbon dianhydride 98,0.9 was heated at 190'C in the presence of 497 g of 3,5-dimethylaniline containing 2.7% by weight of 4-ethoxyaniline and 10.2.9% of anhydrous zinc chloride. After a reaction time of 8 hours, the reaction mixture is diluted with 500 ml of methanol at room temperature and the cocondensation product is subjected to mH in a known manner, giving 149.3 g of α-crystalline phase.

The mass spectrometry crystals correspond to those of Example 3. Example 6 For 2.75 g of 4-ethoxyaniline, an equivalent amount of 4-ethoxyaniline was used.
Using methoxyaniline and otherwise carrying out the procedure as described in Example 2, 58.9 g of the cocondensation product of the α-crystalline modification are obtained.

Example 7 Perylenetetracarboxylic acid dianhydride 7jJ17B, 49(0
, 2 mol), 3,5-dimethylaniline 3879 (3
, 15 mol) and 4-methoxyaniline 12, Og for 7 hours 18 in the presence of 8.19 mol of anhydrous zinc chloride.
Build up the reaction at 0-190"C.

The reaction products formed are then separated using known methods. α−
The yield of cocondensation product present in phase is +18.2 g.

Example 4 (comparative example) 62.0 p of perylenetetracarboxylic dianhydride was added to 3.
Anhydrous zinc chloride in 5-dimethylaniline 210.9 3.
Stir at 185°C in the presence of 22. The resulting bisxylidide of formula (1) is isolated by a conventional method.

Yield is 92.5 g (97.9% of theory),
The reflection angle in the line diffraction pattern (see FIG. 1) agrees with the 1 degree angle data of the crystalline phase of this compound, called the α-modification, which is known from the above-mentioned patent.

Pigment 0.759 and polyethylene ((R)Ho
stalen Go 7260 powder) 500gk001
11n - 200 rpm for 1 minute at room temperature in a high speed mixer
Mix at 0 rotations. (R) Remafin-White R
After addition of CL-hEso (△1% Tie, ) 7°149, the mixture was dried on an extruder (Weber ET20) at 1
Extrude in two steps at 80°C. The resulting granules were subsequently placed in an injection molding machine (Aarburg A11rounaer 2
21E/170P) at test temperature 200-300
The plates are injected at a test temperature of 0.degree. C. with intervals of 20.degree. C. and a residence time of 5 minutes in each case.

Results (A by standard method of tone after DIR No. 53235) The results shown in the table above demonstrate the superior heat resistance of the mixed crystal pigment according to the invention compared to the pure perylene pigment of formula (1). It exhibits a yellowish tone.

[Brief explanation of the drawing]

Claims (1)

[Claims] 1. Mainly the following formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R is a methyl or ethyl group Symmetrical perylenetetracarboxylic acid-bis-3′ represented by
, 5'-dimethylphenylimide and at least one
Perylenetetracarboxylic acid-bis-3',5' of formula (1) consisting of an asymmetrically substituted diimide of formula (2) above
- Perylenetetracarboxylic acid diimide in the crystal lattice of the α-modification of dimethylphenylimide - In a method for producing a mixed crystal pigment, perylenetetracarboxylic dianhydride 1
characterized in that it is condensed with a molar excess of up to 30 molar 3,5-dimethylaniline, which contains a total of 0.5-6% by weight of 4-ethoxyaniline and/or 4-methoxyaniline. The above manufacturing method. 2. The method according to claim 1, wherein 2 to 16 moles of 3,5-dimethylaniline are used per mole of perylenetetracarboxylic dianhydride. 99-97% by weight of 3,3,5-dimethylaniline and 4
3. The method according to claim 1, wherein a mixture of 1-3% by weight of ethoxyaniline is used. 98-94% by weight of 4,3,5-dimethylaniline and 4
- Method according to claim 1 or 2, characterized in that a mixture of 2-6% by weight of methoxyaniline is used. 5. Mainly shown by the following formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, R represents a methyl or ethyl group) Symmetric perylenetetracarboxylic acid-bis-3'
, 5'-dimethylphenylimide and at least one
Perylenetetracarboxylic acid-bis-3',5' of formula (1) consisting of an asymmetrically substituted diimide of formula (2) above
- Perylenetetracarboxylic acid diimide in the crystal lattice of the α-modification of dimethylphenylimide - In a method for producing a mixed crystal pigment, perylenetetracarboxylic dianhydride 1
The product obtained by condensing the molar with up to 30 molar excess of 3,5-dimethylaniline, which contains a total of 0.5-6% by weight of 4-ethoxyaniline and/or 4-methoxyaniline. method for coloring organic polymers.